Aldehyde treatment of land fowl feathers



United States Patent ALDEHYDE TREATMENT OF LAND FOWL FEATHERS VarsenigZ. Pasternak and Robert M. Lollar, Cincinnati, Ohio, assignors to theUnited States of America as represented by the Secretary of the Army NoDrawing. Application May 13, 1957 Serial No. 658,900

12 Claims. (Cl. 894.1)

This invention relates to a method of treating land fowl feathers,especially chicken feathers, to increase their filling power andresiliency, and to impart permanent curliness and water repellency,thereby making such feathers an acceptable substitute for the standarddown and feather mixture now in wide use for sleeping bags, comforters,pillows, etc. A further object is to treat the feathers in such a waythat their enhanced filling power is retained or retained in part afterrepeated launderings. Other objects will be apparent from the [followingdescription of the procedures presently preferred by us.

In explanation of the term filling power, reference may be made to thereport entitled A Proposed Method for Measuring the Filling Power ofDown and Feathers by Henry A. Sinski, publication No. TD-103037, TheOfiice of Technical Services, Department of Commerce, and to the articleby N. B. Edelman in Textile Research Journal, vol. 17, p. 199 (April1947), entitled Investigation of Methods for Determining the FillingPower of Feathers. See also the Sinski et al. Patent No. 2,706,910,dated April 26, 1955. Ordinarily, chicken feathers have a filling powerof 1.8 to 2.1 em., while the 40/60 downfeather mixture has a fillingpower of 5.3 to 5.9 cm.

The term feathers as used herein includes whole land fowl feathers ofthe desired size range, crushed (commercia1curled) land fowl feathers,land fowl feather fibers, stripped land fowl feathers, and mixtures ofthese.

In the Frederick and Jaskowski copending application Ser. No. 411,594,filed February 19, 1954, now Patent No. 2,805,913, acontinuation-in-part of abandoned application Serial No. 359,948, filedJune 5, 1953, a process of lip-grading chicken feathers by means ofglyoxal (diformyl) is disclosed. In the Frederick and Jaskowskicopending application Ser. No. 435,658, filed June 9, 1954, now US.Patent 2,805,914, the treatment of chicken feathers withalpha-hydroxy-adipaldehyde is described and claimed. Both of saidapplications were assigned to the United States Government. The KogaPatent No. 2,129,219, dated September 6, 1938, describes a method ofimproving chicken feathers including two mechanical steps followed bytreatment with formalin vapour.

In the preferred procedure, the feathers, if not known to be entirelyfree from blood, are first soaked for about ten minutes in a watersolution of a commercial blood solubilizer, such as Coagusol (a mixtureof sodium hexametaphosphate and alcohol sulfate). After the soaking, thesolution is drained from the feathers and the feathers are thenlaundered or dry cleaned. In laundering, preferably a detergent such asTergitol NPX (alkyl phenyl ether of polyethylene glycol) is used (0.25%water solution at 110-125 F.) Other non-ionic detergents have been foundto be satisfactory. In general, the nonionic type of detergents shouldbe used to obviate any action on the protein of the feathers. Launderingcontinues for about twenty minutes, then the solution is removed fromthe feathers by centrifuging or wringing. While a number of well knowndry cleaning solutions Patented May 12, 1959 could be used to clean thefeathers, laundering is preferred feathers from the described launderingor dry cleaning operation are placed in a 1% water solution of trisodiumphosphate Na PO .12H O at 43-49 C. for about ten minutes. If feathersfrom mature chickens are being processed, the phosphate treatment periodis increased to about thirty minutes. This mild alkaline treatment ofthe feathers is believed to alter the stability of the feathers bymodification of the cystine linkages in the keratin. This step isimportant because it materially increases the curliness of the feathersand it curls naturally uncurly mature feathers, thereby to increase thebulk value of the final feather product. Other suitably buflferedalkaline solutions, for example, sodium carbonate or borax, may be usedin lieu of the phosphate solution mentioned above, but in all cases thetime of the treatment must be less for immature feathers to avoidexcessive degradation. Trisodium phosphate is preferred because of itsquicker action due to a higher pH. It is believed that the higherconcentration of cystine linkages in mature feathers enables them toresist the action of the alkaline solution for a longer period.

Data of a number of successful laboratory runs at The Tanners CouncilResearch Laboratory, University of Cincinnati, under Contract No.DA-19-l29-QM-23l with the Quartermaster Corps, U.S. Army, will now begiven.

I. Acetaldehyde treatment A batch of washed chicken feathers was giventhe previously described phosphate treatment for thirty minutes at 42-45C., then the feathers were thoroughly rinsed. Next the feathers wereplaced in a bath containing 30 ml. of acetaldehyde (B.P. 21 C.), 1 gramof aluminum sulfate and 1000 ml. of water.

A 40 gram batch of washed chicken feathers was given the previouslydescribed phosphate treatment for thirty minutes at 42-46 C. Then thefeathers were thoroughly rinsed and the wet feathers were placed in abath prepared from 800 ml. of water, 30 g. or 34 ml. of triethylmonomethyl diacetal of malonaldehyde, 200 ml. of 1,4-dioxane and 25 ml.of dilute sulfuric acid, plus 1 gram of aluminum sulfate (chromium orZirconium sulfate). The pH range was 2.7-2.8 and the temperature,42"-45" C. After thirty minutes the pH was raised to 7 and the featherswere allowed to remain in the neutral solution, with occasionalstirring, for an additional thirty minutes at the same temperature. Thenthe feathers were well rinsed, were dried and cured at 87 89 C. for tenutes. The filling power was 6.4, but after laundering filling powerdropped to 5.8.

III. Pyruvicaldehyde treatment A batch of 45' grams of washedchickenfeathers given the previously described phosphate treatment, thenOther normal or basic salts could be used as catalysts in lieu of min--the the feathers were thoroughly rinsed. Then the damp I filling powerof this particular batch of feathers was 5.8;

with a better grade of feathers, the filling power should equal orexceed 6.0.

IV. Butyraldehyde treatment A 40 gram batch of washed chicken featherswas givw en the previously described phosphate soak, then the featherswere thoroughly rinsed. The damp feathers were put in a bath ofbutyraldehyde (butylaldehyde) solution prepared from 30 ml. ofbutyraldehyde, 1000 ml.

of water, 1 gram of aluminum sulfate and enough sulfuric acid to give apH of 2.7-2.8. In lieu of aluminum sulfate, other salts could be used,for example chromium sulfate or zirconium sulfate. The temperature ofthe bath was 42-45 C. for the thirty minutes of the treatment. Then thepH of the bath was raised to slightly V. Succinaldehyde treatment A 45gram batch of washed feathers from cross-breed chickens was soaked in aphosphate bath, as previously described, for thirty minutes at 47 C.,then the feathers were removed and thoroughly rinsed. In the next step,the feathers were put in a bath of succinaldehyde (succindialdehyde)consisting of 60 ml. of 27.6% solution of the aldehyde plus 1000 ml. ofWater. The initial pH was 2.8 without the addition of any outside acid.For thirty minutes the treatment continued at 4245 C., the pH rangingbetween 2.5 and 2.8. Then the pH was raised to 7.0 by adding Na COsolution, and the feathers were kept in the neutral bath for fifteenadditional minutes, at the same temperature. Finally, the feathers wereremoved, thoroughly rinsed, dried, and cured at 87 C. for ten minutes.The filling power for these poor feathers was 5.8; had high qualityfeathers been treated, the filling power undoubtedly would be above 6.0.

VI. Glutaraldehyde treatment A 40 gram batch of washed chicken featherswas given the previously described phosphate treatment for thirtyminutes at 42 46 C. Then the feathers were thoroughly rinsed. The Wetfeathers were put in a bath of 1.8% glutaraldehyde (glutardialdehyde) ina liter of water, to which 0.10.2% of a salt (aluminum sulfate, orchromium sulfate or zirconium sulfate) had been added. The pH range was23. The feathers were kept in the bath for thirty minutes at 42 -45 C.,then the pH was raised to 7.0 by adding Na SO solution and the featherswere held in the bath for fifteen minutes longer. Finally, the featherswere rinsed, tumble dried, and cured at. 89 C. for ten minutes. Thefilling power was 7.1. After laundering, the filling power was 6.4.

VII. Heptaldehyde treatment A 45 gram batch of washed chicken featherswas given the same phosphate soak previously described, then thefeathers were removed and thoroughly rinsed. The wet feathers were putin a bath of ml. of heptaldehyde. (heptyl aldehyde) dissolved in 800 ml.of dioxane, tov which 1 gram of aluminum sulfate and 200 ml. of waterwere added. The bath was made acidic with dilute sulacid, the pH being2.7 to 2.8, while the temperature 4 was 42 -45 C. After thirty minutes,the pH was raised to 7 by adding Na CO solution and the feathers werekept in the bath for 15 minutes longer. The feathers were re moved andsoaked in dioxane, then they were rinsed, dried and cured for tenminutes at 8892 C. The filling power was 5.2, but after laundering, thefilling power was measured at 5.8.

VIII. Furfural (Z-furaldehyde) treatment A 45 gram batch of washedchicken feathers was soaked in the previously described phosphatesolution for thirty minutes, then the feathers were removed andthoroughly rinsed. The damp feathers were immersed in 1000 ml. of a 2%furfural solution, to which 1 gram of aluminum sulfate had been added,plus enough dilute sulfuric acid to make the pH 2.7 to 2.8. Thetemperature of the bath was 4245 C. and the feathers were kept in it50-60 minutes. Then the pH was raised to 7.0 by adding Na CO solution,and the feathers were kept in the bath for fifteen minutes longer at42-45 C. Finally, the feathers were removed, well rinsed, dried andcured at about 90 C. The filling power was 6.1; and after laundering thefeathers, the filling power was again read as 6.1.

IX. Benzaldehyde treatment A 40 gram batch of washed chicken featherswas giventhe previously described phosphate soak for thirty minutes,then the feathers were thoroughly rinsed. The wet feathers were immersedin a bath composed of 19 ml. of benzaldehyde (benzoic aldehyde), 200 ml.of dioxane, 800 m1. of water, 1 gram of aluminum sulfate (or other saltas mentioned above), and enough sulfuric acid to give a pH of 2.7. Thetreatment may continue for 30 to 60 minutes at 42-45 C. Then the pH israised to 7.0 by adding Na CO solution, and the feathers are kept in theneutral solution for fifteen minutes at 42-45 CL Finally, the feathersare removed, rinsed, dried and cured at about 90 C. The filling powerwas 6.2; and after laundering, the filling power was 6.1.

X. Anisaldehyde treatment A 40 gram batch of washed chicken feathers wasgiven the same thirty minutes phosphate soak previously described, thenthe feathers were removed and thoroughly rinsed. The wet feathers wereimmersed in a bath of. 21 ml. of anisaldehyde (anisic aldehyde) in 200ml. of 1,4-dioxane and 800 ml. of water, with 1 gram of a salt; such asaluminum sulfate, plus enough dilute sulfuric acid to maintain a pH ofbetween 2 and 3.0. The temperature was 4245 C. and the treatmentcontinued for not over sixty minutes for best results. A fifty minutetreatment will give good results. Next the pH was raised to 7.0 forfifteen minutes, the temperature remaining the same. Finally, thefeathers are removed, rinsed well, dried and cured at about 90 C. Thefilling power was 5.7, but after laundering, the filling power rose to5.9.

XI. Salicyladehyde treatment A 40 gram batch of washed chicken featherswas given the phosphate soak previously described, then the featherswere thoroughly rinsed. The wet feathers were put in a bath consistingof 19 ml. of salicylaldehyde (salicylic aldehyde) in 400 ml. of1,4-dioxane and 600ml. of water. The dioxane in this example, as in theothers given above, was used to make the heavier aldehyde more solublein water. One gram of a salt such as aluminum sulfate, chromium sulfateor zirconium sulfate was added to the bath'plus enough dilute sulfuricacid to make the pH 2.7-2.8. The treatment may be between thirty andsixty minutes at 42-45 C. Then the bath was neutralized by adding Na COsolution, and the feathers were allowed filling power reading was 6.0,but after laundering the feathers, the reading was 6.4.

Other aldehyde treatments Chicken feathers have also been treated withacrolein (acrylic aldehyde) with remarkable results. Acrolein is anunsaturated aldehyde and may be polymerized in situ, using light as thecatalytic agent. The copending application of Varsenig Z. Pasternak,Ser. No. 654,617, filed April 23, 1957, entitled Acrolein Treatment ofFeathers, should be referred to in this connection.

Other aldehydes presumably will react with the feather keratin to givegood filling power measurements, for example, propionic aldehyde(propanal), crotonic aldehyde (propylene aldehyde), and cuminaldehyde(cuminal).

Having thus described the practice of our invention by means of severalactual examples for carrying out the same, we now define the scope ofour invention by the appended claims.

Having described our invention, we claim:

1. A method of treating land fowl feathers to enhance their fillingpower, which comprises placing the land fowl feathers for about 30-60minutes in an aqueous bath of an aldehyde selected from the groupconsisting of succinaldehyde, pyruvicaldehyde, acetaldehyde,malonaldehyde, butyraldehyde, glutaraldehyde, heptaldehyde, furfural,benzaldehyde, anisaldehyde, and salicylaldehyde, the last nine membersof said group being in the presence of a catalyst, said catalyst being ametal salt present in a catalytic amount; said bath having a pH of about2-3, and said bath being warmed above room temperature when saidaldehyde is a member of said group of aldehydes other than acetaldehyde;then raising the pH of the bath to substantially neutral and keepingsaid feathers in said substantially neutral bath until the filling powerof said feathers is increased; then rinsing the feathers and dryingthem.

2. The method according to claim 1, wherein said metal salt catalyst isa member of the group consisting of aluminum sulfate, chromium sulfateand zirconium sulfate.

3. The method according to claim 1, wherein said aldehyde isacetaldehyde.

4. The method according to claim 1, wherein said aldehyde isbutyraldehyde.

5. The method according to claim 1, wherein said a1- dehyde isglutaraldehyde.

6. The method according to claim 1, wherein said aldehyde is furfural.

7. The method according to dehyde is salicylaldehyde.

8. The method according to claim 1, wherein the cystine linkage of thekeratin of said land fowl feathers is modified, prior to said aldehydetreatment, by immersing said feathers in an aqueous alkaline solutionuntil their curliness is increased, and rinsing said feathers after saidimmersion.

9. The method according to claim 8, wherein said aqueous alkalinesolution is an approximately 1% solution of trisodium phosphate having atemperature of about 43-49 C., said immersion having a duration of about10-30 minutes.

10. A method of treating land fowl feathers to enhance their fillingpower, which comprises placing the land fowl feathers in an aqueous bathof acetaldehyde in the presence of a catalytic amount of a metal saltcatalyst, at a pH of about 2.7-2.8 for about 30 minutes, then raisingthe pH of the bath to substantially neutral and keeping said feathers insaid substantially neutral bath until the filling power of said feathersis increased, then rinsing the feathers and drying them at a temperaturesubstantially above room temperature.

11. The method according to claim 10, wherein said metal salt catalystis a member of the group consisting of aluminum sulfate, chromiumsulfate and zirconium sulfate.

12. The method according to claim 10, wherein the cystine linkage of thekeratin of said land fowl feathers is modified, prior to saidacetaldehyde treatment, by immersing said feathers in an aqueousalkaline solution until their curliness is increased, and rinsing saidfeathers after said immersion.

claim 1, wherein said al- References Cited in the file of this patentUNITED STATES PATENTS 2,108,520 Wolf Feb. 15, 1938 2,129,219 Koga Sept.16, 1938 2,389,292 Bjorksten Nov. 20, 1945 2,499,444 Allison Mar. 7,1950 2,524,042 Croston Oct. 3, 1950 2,547,060 Tillisch Apr. 3, 19512,583,574 Jones Jan. 29, 1952 2,805,913 Frederick Sept. 10, 19572,805,914 Frederick Sept. 10, 1957 V UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION.

atent No, 2,886,399

Varsenig Zo Pasternak et ale May 12, 1959 It is hereby certified thaterror appears in the printed specification If the above numbered patentrequiring correction and that the said Letters atent should read ascorrected below.

Column 3, line 61, for "Na SO solution" read Nat 00 solution Signed andsealed this 29th day of September 1959,

:SEAL) kt'test:

KARL Ho .AXLINE kttesting Officer ROBERT C. WATSON Commissioner ofPatents

1. A METHOD OF TREATING LAND FOWL FEATHERS TO ENHANCE THEIR FILLINGPOWER, WHICH COMPRISES PLACING THE LAND FOWL FEATHERS FOR ABOUT 30-60MINUTED IN AN AQUEOUS BATH OF AN ALEHYDE SELECTED FROM THE GROUPCONSISTING OF SUCCINALDEHYDE, PYRUVICALDEHYDE, ACETALDEHYDE,MALONALDEHYDE, OUTYRALDEHYDE, GLUTHRALDEHYDE,HEPTALDEHYDE, FURFURAL,BENZALDEHYDE, ANISALDEHLYDE, AND SALICYLALKEHYDE, THE LAST NINE MEMBEROF SAID GROUP BEING IN THE PRESENCE OF A CATALYST, SAID CATALYST BEING AMETAL SALT PRESENT IN A CATALYST AMOUNT; SAID BATH HAVING A PH OF ABOUT2-3 AND SAID BATH BEING WARMED ABOVE ROOM TEMPERATURE WHEN SAID ALDEHYDEIS A MEMBER OF SAID GROUP OF ALDE HYDES OTHER THAN ACETALDEHYDE; THENRAISING THE PH OF THE BATH TO SUBSTANTIALLY NEUTRAL AND KEEPING SAIDFEATHER IN SAID SUBSTANTIALLY NEUTRAL BATH UNTIL THE FILLING POWER OFSAID FEATHERS IS INCREASED; THEN RINSING THE FEATHERS AND DRYING THEM.3. THE METHOD ACCORDING TO CLAIM 1, WHEREIN SAID ALDEHYDE ISACETALDEHYDE.